Photographic material containing filter dyes

ABSTRACT

This invention relates to new polymethinoxanol dye-stuffs. They correspond to the formula   WHEREIN X is the residue of a heterocyclic ring system and R1 and R2 are hydrogen atoms or optionally substituted alkyl or aryl groups. They are useful for incorporation in photographic silver halide material and able to correct various deficiencies of such material.

United States Patent H 1 MacDonald et al.

[54] PHOTOGRAPHIC MATERIAL CONTAINING FILTER DYES [75] Inventors: Eric MacDonald, Llanbrynmair, Wales; Frederick Campbell, Manchester, both of England [73] Assignee: lliord Limited, llford, England [22] Filed: June 2, 1971 [2]] Appl. No.: 149,398

[30] Foreign Application Priority Date June 3, 1970 Great Britain ..26,84l/70 [52] US. Cl. ..96/84 R, 260/2402 [51] Int. Cl. ..G03c 1/84 [58] Field of Search ..96/84 R [56] References Cited UNITED STATES PATENTS 2,611,696 9/1952 Keyes et al ..96/84 R 2,533,472 12/1950 Keyes et al ..96/84 R 1 Mar. 27, 1973 Primary Examiner-Ronald H. Smith Att0rneyWender0th, Lind & Ponack [57] ABSTRACT This invention relates to new polymethinoxanol dyestuffs. They correspond to the formula llO 4 Claims, No Drawings PHOTOGRAPIIIC MATERIAL CONTAINING FILTER DYES This invention relates to novel dyestuffs and to their use in photographic materials.

According to the present invention there is provided a dyestuff of the general formula I:

with a compound of formula III:

M IO

The dyestuffs of the present invention are of use as filter dyes in photographic silver halide materials and according to another aspect of the present invention there is provided photographic silver halide material which comprises a support having coated thereon at least one silver halide emulsion layer there being present in at least one layer of the photographic material at least one dyestuff of the above formula I.

The use of dyes in gelatin layers (or other polymeric layers) or gelatino silver halide emulsion layers of photographic materials is well known to correct for various inherent deficiencies of photographic material. Such deficiencies are for example:

a. the U.V. sensitivity of most silver halide layers (which however can be corrected by the U.V. absorbing filters on the camera lens),

b. in conventional order multilayer color camera material, the blue sensitivity of the green and red sensitive layers,

c. progressive scatter of light by the silver halide grains leading to unsharpness (loss of acutance),

d. reflection oflight at the emulsion-base, base-air interfaces (halation),

e. multilayer color material out of speed balance,

I. non-ideal spectral sensitivity.

Such dyes may be called filter, untihulution, screening, layer balancing or ucutuncc dyes, depending on their function. They all act by absorbing light to which a particular silver halide emulsion is sensitive, and they can be multifunctional. Dyes of this type may be diwherein X, R and R, have the meanings assigned to them above, in an organic solvent in the presence of a basic condensing agent.

vided into two classes:

1. those which are non-diffusible and which therefore may be located in a particular layer or silver halide emulsion layer or layers,

2. those which are freely diffusible.

Whatever the function of the dye or its class, it must satisfy the following requirements:

a. the dye must have the correct selective spectral absorption for the function to be performed,

b. the dyes must be photographically inert, i.e., have no chemical desensitizing or fogging action,

c. in the case of photographic material for viewing as a transparency, the dye must be completely removable at some stage in the processing procedure. The removal can be by destruction of the color chromophore of a non-diffusible dye, or by washing out of a soluble diffusible dye which preferably is accompanied by decolorization, otherwise baths can become undesirably colored.

The dyes of the present invention have been found to be of use in correcting a number of the inherent deficiencies of silver halide photographic material as hereinbefore set forth. They are all of class 1 gelatin substantive type and satisfy the requirements (a), (b) and (c) as hereinbefore set forth. They have little or no effect on the sensitivity of green and red sensitized layers over and above the decrease expected by absorption of light to which the layers are sensitive. They have no fogging effect on silver halide emulsions. Although substantive to the photographic layer in which they are coated, they are rapidly removed and permanently decolorized by the sodium sulphite present in most photographic developers.

The following preparations will serve to illustrate the preparations of some of the intermediates used in the Examples which follow.

3 4 l-Phenyl-3-methyl-4-'y-acetanilidoallylidene-S- CO(|JH; pyrazolone (Jul (DH-(35H:

CH3 COCHI 60- H2 I I u N C=CH CH=CH N Prepared by the condensation of benzylldene Gi acetone with sodiodiethyl malonate followed by alkaline hydrolysis. Colorless crystals m.p. 180 (dec.).

17.4 parts of l-phenyl-3-methyl-5-pyrazalone and s'p'Anisoylcyclohexanel:3'd'one 25.85 parts of B-anilinoacrolein anil hydrochloride, I were mixed in 100 parts of acetic anhydride and 10.1 (L m parts of triethylamine cautiously added with stirring. Hz 4 OCH1 The solution so obtained was refluxed for 30 minutes OAJJH and cooled. The crystalline solid collected by filtration l5 2 was washed with ether and recrystallized from toluene. 18.3 parts of the orange-red crystalline solid m.p. 213 22 were obtained. Prepared by the I condensation of p-anislyidene 1 A i 3- 1 4 1 acetone with sodiodiethyl malonate followed by alpyrazolone kaline hydrolysis. Colorless crystalls m.p. 176.

7 Z-y-amlrdoallylrdene-S:5-dimethylcyclohexane-1:3-

CH8 dione COCH:

Replacing 17.4 parts of l-phenyl-3-methyl-5- pyrazolone by 20.4 parts of l-p-anisoyl-3-methyl-5- pyrazolone in the above preparation, 14.8 parts ofa 11.2 parts of dimedone and 11.4 parts of B- crystalline lid mp- 15 were Obtainedanilinoacrolein anil hydrochloride were dissolved in l-p-Tolyl-3-methyl-4-ynili llyli 200 parts of hot ethanol and 20 parts of triethylamine pyrazo n then refluxed for 15 minutes during which time the crystalline product separated. This was collected by fil- COCH; tration. Recrystallization from ethanol yielded 6.8 parts of a yellow crystalline solid m.p. 207 which analyzed C=CH CH=CH N as follows: a 0 Found C 75.6%; H 6.4%; N 5.0%. C -,H, O N

requires C 75.8%; H 7.1%; N 5.2%. Replacing 17.4 parts of l-phenyl-3-methyl-5- 40 In Examples l-3 which follow, dyestuffs of the folpyrazolone by 18.8 parts of l-p-tolyl-3-methyl-5- lowing general formula were prepared:

C O-CH:

pyrazolone, 16.8 parts ofa crystalline solid m.p. 2024 The value of R is indicated in each specific Example.

were obtained. The following Examples will serve to illustrate the in- Z-y-acetanilidoallylidene-l:B-indandione vention.

o0 Coon,

EXAMPLE 1 00 [l-phenyl-3-methyl-5-pyrazolone-(4)]-[S-p-anisoylcyclohexane- 1 :3-dione-(2)]trimethinoxonol. (R H) 30 parts of indandione, 51 parts of B-anilinoacrolein 1 of -P y y -vyanil hydrochloride, 18.0 parts of anhydrous potassium -pyr zolone, 175 parts of S-p-anisoylacetate and 300 parts of acetic anhydride were refluxed y were refluxed for 2 u in 800 for 15 minutes and cooled. The product was collected P of ethanol and Parts of triethylamine- The by filtration and washed with wat h l d solution so obtained was poured into excess of cold finally ether. 57.5 parts of a yellow crystalline solid Water and hydrochloric acid- 313 Parts ofa brownish m.p. 242-3 analyzed as follows; solid was collected by filtration m.p. 208-2 1 0. A sam- F nd C 753%; H 43%; N C r- MO 65 ple recrystallized from dimethylformamide analyzed as requires C 75.7%; H 4.7: N 15.2%. fOIlOWSI 5-Phenyldihydroresorcinol (or S-phenylcyclohexane- Found 1 C 732%; H 54%; N 2a 2a z 4 lit-dione) requires C 73.1%; H 5.4%; N 6.5%.

EXAMPLE 3 [l-p-tolyl-3-methyl-5 -pyrazolone-(4 S-p-anisoylcyclohexane-l:3-dione-(2)ltrimethinoxonol (R CH Replacing the substituted pyrazolone in the Examples l and 2 with 14.4 parts of l-p-tolyl-3-methyl'4-yacetanilido allylidene--pyrazolone, 15.4 parts of the above product, m.p. 216, were obtained.

EXAMPLE 4 [1:3-indandione-(2)]-[5:S-dimethylcyclohexanel :3- dione-(2)ltrimethinoxonol This was made in two ways:

1. 3.2 parts of Z-y-acetanilidoalkylidene-lz3-indandione, 1.9 parts of dimedone, parts of pyridine and L5 parts of triethylamine were heated for 1 hour on the steam bath, cooled and poured into an excess of water and hydrochloric acid. The product was collected by filtration and well washed with water (3.1 parts). On recrystallization from butanol the product melted at 2. 2.7 parts of Z-y-anilidoallylidene-S:S-dimethyllz3-dione, 1.46 parts of indandione, 20 parts of pyridine and 1.5 parts of triethylamine were heated for one hour on the steam bath, cooled and poured into an excess of water and hydrochloric acid. The product was collected by filtration and well washed with water (3.3 parts). 0n recrystallization from butanol product melted at 240.

[1:3-indandione-(2)]-[5-phenylcyclohexane-l :3- dione-(2)]-trimethinoxonol 34.l parts of 2--y-acetanilidoallylidene-l:3-indandione and 21 parts of 5-phenyl-cyclohexane-l:3-dione were heated in 250 parts of pyridine until dissolved and- 14 parts of triethylamine added. After refluxing for 1 hour the solution was cooled and drowned into an excess of water and hydrochloric acid. The solid collect by filtration, 46 parts, was heated with butanol and refiltered hot and washed with petrol ether to give a crystalline product m.p. 238 -242 which analyzed as follows:

Found C 78.4%; H 5.3%; Required C 77.8%; H

EXAM PLE 6 Incorporation in Gelatin Filter Layer The dyestuffs of the Examples were incorporated in photographic material in the following manner:

2 parts of the dye were dissolved by warming in parts of methanol containing 10 parts of 2N sodium carbonate solution. The solution was added with stirring to a solution at 40 of 400 parts of 10 percent gelatin solution, parts of water and 10 parts of 4 percent methanolic solution of the dioctyl ester of sodium sulfosuccinic acid, and the pH reduced to 6.3 with a normal solution of acetic acid. The gelatin layer was coated by conventional means as a photographic filter layer between two gelatino emulsion layers in photographic multilayer material. The dyes of the Examples exhibited the following spectral characteristics in the filter layer.

Example Absorption Maximum (mp) Maurowherein X is the residue of a pyrazolone or indanedione ring system, R is an alkyl group or a hydrogen atom, R is a hydrogen atom, an alkyl group or an aryl group.

2. Photographic material as claimed in claim 1,

which contains a polymethinoxanol dyestuff of the formula wherein 2 represents a member selected from the L group consisting of a hydrogen atom, a methyl group X=CHCH=CHC c and a methoxy t I 4. Photographic maternal as claimed in claim 1 which C CH' 5 contains a polymethinoxanol dyestuff of the formula H 51 wherein X represents a radical selected from the group C I consis mg of the heterocycllc radica s of the formulas l0 C:CH CH=CH U C A g c J: and wherein U represents a member selected from the I; group consisting of the radicals corresponding to the fon'nulas Y denoting a benzene radical, R represents a member 0 i i 0 selected from the group consisting of a hydrogen atom and a lower alkyl group, and R represents a member g H selected from the group consisting of a hydrogen atom, and

a lower alkyl group and a benzene radical. /CCH1 CH3 /CCH2 3. Photographic material as claimed in claim 1 which H0 H0 contains a polymethinoxanol dyestuff of the formula CH3 [0 /(B\ JCHz H 111/ C=CHCH=CHC\ /C z-N- c=o C-CH1 

2. Photographic material as claimed in claim 1, which contains a polymethinoxanol dyestuff of the formula
 3. Photographic material as claimed in claim 1 which contains a polymethinoxanol dyestuff of the formula
 4. Photographic material as claimed in claim 1 which contains a polymethinoxanol dyestuff of the formula 